EP1115011A1 - Radiation image sensor - Google Patents

Radiation image sensor Download PDF

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Publication number
EP1115011A1
EP1115011A1 EP99925376A EP99925376A EP1115011A1 EP 1115011 A1 EP1115011 A1 EP 1115011A1 EP 99925376 A EP99925376 A EP 99925376A EP 99925376 A EP99925376 A EP 99925376A EP 1115011 A1 EP1115011 A1 EP 1115011A1
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EP
European Patent Office
Prior art keywords
scintillator
imaging device
film
substrate
image sensor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP99925376A
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German (de)
French (fr)
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EP1115011A4 (en
EP1115011B1 (en
Inventor
Toshio Takabayashi
Takuya Homme
Hiroto Sato
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Hamamatsu Photonics KK
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Hamamatsu Photonics KK
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01TMEASUREMENT OF NUCLEAR OR X-RADIATION
    • G01T1/00Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
    • G01T1/16Measuring radiation intensity
    • G01T1/20Measuring radiation intensity with scintillation detectors
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01TMEASUREMENT OF NUCLEAR OR X-RADIATION
    • G01T1/00Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
    • G01T1/16Measuring radiation intensity
    • G01T1/20Measuring radiation intensity with scintillation detectors
    • G01T1/2002Optical details, e.g. reflecting or diffusing layers

Definitions

  • the present invention relates to a radiation image sensor used for medical X-ray photography and the like.
  • X-ray sensitive films have been used in medical and industrial X-ray photography
  • radiation imaging systems using radiation detecting devices have been coming into wider use from the viewpoint of convenience and their storability of photographed results.
  • pixel data caused by two-dimensional radiation are acquired by a radiation detecting device as an electric signal, which is then processed by a processing unit, so as to be displayed onto a monitor.
  • a typical radiation detecting device is one disclosed in WO92/06476.
  • a scintillator formed on a substrate and an imaging device are bonded together with an adhesive, such that the radiation incident from the substrate side is converted into visible light by the scintillator, so as to be detected.
  • the present invention provides a radiation image sensor comprising a scintillator panel and an imaging device; wherein the scintillator panel comprises a radiation-transparent substrate, a scintillator formed on the substrate, and an elastic organic film covering the scintillator; and wherein the scintillator panel and the imaging device are superposed on each other with an optical coupling material interposed therebetween, side wall portions of the scintillator panel and imaging device being firmly attached to each other with a resin.
  • the scintillator since the scintillator is covered with an elastic organic film and is superposed onto the imaging device with an optical coupling material interposed therebetween, the impact acting on the scintillator can be alleviated by way of the elastic organic film when bonding the scintillator panel to the imaging device, whereby the scintillator can be prevented from being damaged. Also, even when a distortion is generated in the substrate due to temperature changes, since the scintillator is covered with the elastic organic film, the stress acting on the scintillator according to the distortion of substrate can be alleviated by the elastic organic film, whereby the scintillator can be prevented from being damaged.
  • the present invention is characterized in that the scintillator of radiation image sensor has a columnar structure.
  • the tip portion of the scintillator having a columnar structure is covered with the elastic organic film, the impact acting on the tip portion of the scintillator having a columnar structure when superposing the scintillator panel onto the imaging device and the stress acting on the scintillator according to the distortion caused by temperature changes can be alleviated, whereby the tip portion of the scintillator having a columnar structure can be prevented from being damaged.
  • Fig. 1 is a sectional view of a radiation image sensor 2 in accordance with an embodiment of the present invention.
  • the radiation image sensor 2 has a configuration in which a scintillator panel 4 and an imaging device 6 are bonded to each other and are accommodated in a ceramic case 8.
  • one surface of a substrate 10 made of Al in the scintillator panel 4 is formed with a scintillator 12, having a columnar structure, for converting incident radiation into visible light.
  • a scintillator 12 CsI doped with Tl is used. All surfaces of the scintillator 12 formed on the substrate 10, together with the substrate 10, are covered with a first polyparaxylylene film (first organic film) 14 having an elasticity, whereas the surface of first polyparaxylylene film 14 on the scintillator 12 side is formed with an SiO 2 film (transparent inorganic film) 16.
  • the surface of SiO 2 film 16 and the surface of the part of first polyparaxylylene film 14 not formed with the SiO 2 film 16 on the substrate 10 side are formed with a second polyparaxylylene film (second organic film) 18, whereby all surfaces are covered with the second polyparaxylylene film 18.
  • second polyparaxylylene film second organic film
  • the imaging device 6 is attached to the scintillator panel 4 on the scintillator 12 side with a silicone resin layer 20, as a matching oil, interposed therebetween, whereas the bottom part of imaging device 6 is accommodated in a cavity portion 8a of the ceramic case 8.
  • a silicone resin layer 20 as a matching oil
  • an optical coupling material such as a silicone potting gel exemplified by Sylgard® available from Dow Corning Corporation is used.
  • side wall portions of the scintillator panel 4 and imaging device 6 are fixed to each other by a resin 24 for protecting a bonding wire 22 and fixing the scintillator plate 4 to the ceramic case 8.
  • a rectangular substrate 10 having a thickness of 0.5 mm
  • columnar crystals of Tl-doped CsI are grown by vapor deposition method, whereby the scintillator 12 is formed by a thickness of 200 ⁇ m (see Fig. 2B).
  • the first polyparaxylylene film 14 is formed by CVD method in order to prevent this from occurring. Namely, the substrate 10 formed with the scintillator 12 is put into a CVD apparatus, so as to form the first polyparaxylylene film 14 by a thickness of 10 ⁇ m. As a consequence, the first polyparaxylylene film 14 is formed on all surfaces of the scintillator 12 and substrate 10 (see Fig. 2C). Since the tip portion of scintillator 12 is uneven, the first polyparaxylylene film 14 also functions to flatten the tip portion of scintillator 12.
  • the SiO 2 film 16 is formed on the surface of first polyparaxylylene film 14 on the scintillator 12 side with a thickness of 200 nm by sputtering (see Fig. 3A).
  • the SiO 2 film 16 is formed in an area covering the scintillator 12, since it is aimed at improving the moisture resistance of scintillator 12. Since the tip portion of scintillator 12 is flattened by the first polyparaxylylene film 14 as mentioned above, the SiO 2 film can be formed thinner (with a thickness of 100 nm to 300 nm) so that the output light quantity would not decrease.
  • the second polyparaxylylene film 18 for preventing the SiO 2 film 16 from peeling is formed with a thickness of 10 ⁇ m by CVD method on the surface of SiO 2 film 16 and the surface of first polyparaxylylene film 14 not formed with the SiO 2 film 16 on the substrate 10 side (see Fig. 3B).
  • the making of scintillator panel 4 ends.
  • the imaging device 6 is attached to the scintillator panel 4 on the scintillator 12 side with the silicone resin layer 20 interposed therebetween. Also, the bottom part of the imaging device 6 attached to the scintillator panel 4 is accommodated in the cavity portion 8a of ceramic case 8, whereas a pad portion of the imaging device 6 and a lead pin secured to the ceramic case 8 are electrically connected to each other with a bonding wire 22. Then, for protecting the bonding wire 22 and securing the scintillator plate 4 to the ceramic case 8, side wall portions of the scintillator panel 4 and imaging device 6 are fixed with the resin 24. When this step is completed, the making of the radiation image sensor 2 shown in Fig. 1 ends.
  • the scintillator 12 since the scintillator 12 is covered with the first polyparaxylylene film 14 and is attached to the imaging device 6 with the silicone resin 20 interposed therebetween, the impact acting on the tip portion of scintillator 12 when bonding the scintillator panel 4 to the imaging device 6 can be alleviated by the first polyparaxylylene film 14, whereby the tip portion of scintillator 12 can be prevented from being damaged.
  • the scintillator 12 is covered with the first polyparaxylylene film 14 since the scintillator 12 is covered with the first polyparaxylylene film 14, the stress acting on the scintillator 12 according to the distortion of substrate 10 can be alleviated by the first polyparaxylylene film 14, whereby the scintillator 12 can be prevented from being damaged.
  • silicone resin 20 is used as the matching oil (optical coupling material) in the above-mentioned embodiment, it is not restrictive; and epoxy resin, silicone oil, and the like may also be used.
  • the SiO 2 film is used as the transparent inorganic film 16, it is not restrictive; and inorganic films made from Al 2 O 3 , TiO 2 , In 2 O 3 , SnO 2 , MgO, MgF 2 , LiF, CaF 2 , SiNO, AgCl, SiN and the like may also be used.
  • CsI(Tl) is used as the scintillator 12 in the above-mentioned embodiment, it is not restrictive; and CsI(Na), NaI(Tl), LiI(Eu), KI(Tl), and the like may also be used.
  • any substrate can be used as long as it has a favorable X-ray transmissivity, whereby substrates such as those made of amorphous carbon mainly composed of carbon, those made of C (graphite), those made of Be, those made of SiC, and the like may also be used.
  • the scintillator 12 is covered with the first polyparaxylylene film 14, SiO 2 film 16, and second polyparaxylylene film 18 in the above-mentioned embodiment, it may be covered with the first polyparaxylylene film 14 alone or with the first polyparaxylylene film 14 and SiO 2 film 16. Since the first polyparaxylylene film 14 in contact with the scintillator 12 has an elasticity, the scintillator 12 can also be prevented from being damaged in this case as in the radiation image sensor 2 in accordance with the above-mentioned embodiment.
  • C-CCD cooling type imaging device
  • polyparaxylylene film in the above-mentioned embodiment not only polyparaxylylene but also polymonochloroparaxylylene, polydichloroparaxylylene, polytetrachloroparaxylylene, polyfluoroparaxylylene, polydimethylparaxylylene, polydiethylparaxylylene, and the like can be used.
  • the scintillator since the scintillator is covered with an elastic organic film and is superposed onto the imaging device with a matching oil interposed therebetween, the impact acting on the scintillator can be alleviated by way of the elastic organic film when superposing the scintillator panel onto the imaging device, whereby the scintillator can be prevented from being damaged. Also, even when a distortion is generated in the substrate due to temperature changes, since the scintillator is covered with the elastic organic film, the stress acting on the scintillator according to the distortion of substrate can be alleviated by the elastic organic film, whereby the scintillator can be prevented from being damaged.
  • the radiation image sensor in accordance with the present invention is suitably usable for medical and industrial X-ray photography and the like.

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Molecular Biology (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Measurement Of Radiation (AREA)

Abstract

In a radiation image sensor (2) comprising a scintillator panel (4) and an imaging device (6), the scintillator panel (4) comprises a radiation-transparent substrate (10), a deliquescent scintillator (12) formed on the substrate (10), and an elastic organic film (14) covering the scintillator (12), the scintillator panel (4) and imaging device (6) being bonded to each other with a matching oil (20) interposed therebetween, whereas side wall portions of the scintillator panel (4) and imaging device (6) are firmly attached to each other with a resin (24).

Description

    Technical Field
  • The present invention relates to a radiation image sensor used for medical X-ray photography and the like.
  • Background Art
  • While X-ray sensitive films have been used in medical and industrial X-ray photography, radiation imaging systems using radiation detecting devices have been coming into wider use from the viewpoint of convenience and their storability of photographed results. In such a radiation imaging system, pixel data caused by two-dimensional radiation are acquired by a radiation detecting device as an electric signal, which is then processed by a processing unit, so as to be displayed onto a monitor.
  • Conventionally known as a typical radiation detecting device is one disclosed in WO92/06476. In this radiation detecting device, a scintillator formed on a substrate and an imaging device are bonded together with an adhesive, such that the radiation incident from the substrate side is converted into visible light by the scintillator, so as to be detected.
  • Meanwhile, individual columnar crystals of the scintillator formed on the substrate have different heights, thus yielding unevenness, whereby the tip portion of scintillator might collide with the light-receiving surface of imaging device when being bonded to the imaging device, thereby being damaged. Also, when the imaging device and the scintillator are firmly attached to each other with an adhesive, a distortion may occur in the substrate due to temperature changes, thereby causing a damage to columnar crystals of the scintillator. In the case where a cooling type CCD is used for the imaging device in particular, the distortion becomes greater upon drastic temperature changes, whereby the scintillator is more likely to be damaged.
  • It is an object of the present invention to provide a radiation image sensor which can prevent the scintillator from being damaged.
  • Disclosure of the Invention
  • The present invention provides a radiation image sensor comprising a scintillator panel and an imaging device; wherein the scintillator panel comprises a radiation-transparent substrate, a scintillator formed on the substrate, and an elastic organic film covering the scintillator; and wherein the scintillator panel and the imaging device are superposed on each other with an optical coupling material interposed therebetween, side wall portions of the scintillator panel and imaging device being firmly attached to each other with a resin.
  • According to the present invention, since the scintillator is covered with an elastic organic film and is superposed onto the imaging device with an optical coupling material interposed therebetween, the impact acting on the scintillator can be alleviated by way of the elastic organic film when bonding the scintillator panel to the imaging device, whereby the scintillator can be prevented from being damaged. Also, even when a distortion is generated in the substrate due to temperature changes, since the scintillator is covered with the elastic organic film, the stress acting on the scintillator according to the distortion of substrate can be alleviated by the elastic organic film, whereby the scintillator can be prevented from being damaged.
  • Also, the present invention is characterized in that the scintillator of radiation image sensor has a columnar structure. According to the present invention, since the tip portion of the scintillator having a columnar structure is covered with the elastic organic film, the impact acting on the tip portion of the scintillator having a columnar structure when superposing the scintillator panel onto the imaging device and the stress acting on the scintillator according to the distortion caused by temperature changes can be alleviated, whereby the tip portion of the scintillator having a columnar structure can be prevented from being damaged.
  • Brief Description of the Drawings
  • Fig. 1 is a sectional view of the radiation image sensor in accordance with an embodiment of the present invention;
  • Fig. 2A is a view showing a step of making a scintillator panel in accordance with an embodiment of the present invention;
  • Fig. 2B is a view showing a step of making the scintillator panel in accordance with an embodiment of the present invention;
  • Fig. 2C is a view showing a step of making the scintillator panel in accordance with an embodiment of the present invention;
  • Fig. 3A is a view showing a step of making the scintillator panel in accordance with an embodiment of the present invention; and
  • Fig. 3B is a view showing a step of making the scintillator panel in accordance with an embodiment of the present invention.
  • Best Mode for Carrying Out the Invention
  • In the following, with reference to Figs. 1 to 3B, embodiments of the present invention will be explained. Fig. 1 is a sectional view of a radiation image sensor 2 in accordance with an embodiment of the present invention. As shown in Fig. 1, the radiation image sensor 2 has a configuration in which a scintillator panel 4 and an imaging device 6 are bonded to each other and are accommodated in a ceramic case 8.
  • Here, one surface of a substrate 10 made of Al in the scintillator panel 4 is formed with a scintillator 12, having a columnar structure, for converting incident radiation into visible light. As the scintillator 12 CsI doped with Tl is used. All surfaces of the scintillator 12 formed on the substrate 10, together with the substrate 10, are covered with a first polyparaxylylene film (first organic film) 14 having an elasticity, whereas the surface of first polyparaxylylene film 14 on the scintillator 12 side is formed with an SiO2 film (transparent inorganic film) 16. Further, the surface of SiO2 film 16 and the surface of the part of first polyparaxylylene film 14 not formed with the SiO2 film 16 on the substrate 10 side are formed with a second polyparaxylylene film (second organic film) 18, whereby all surfaces are covered with the second polyparaxylylene film 18.
  • On the other hand, the imaging device 6 is attached to the scintillator panel 4 on the scintillator 12 side with a silicone resin layer 20, as a matching oil, interposed therebetween, whereas the bottom part of imaging device 6 is accommodated in a cavity portion 8a of the ceramic case 8. As the matching oil, an optical coupling material such as a silicone potting gel exemplified by Sylgard® available from Dow Corning Corporation is used. Further, side wall portions of the scintillator panel 4 and imaging device 6 are fixed to each other by a resin 24 for protecting a bonding wire 22 and fixing the scintillator plate 4 to the ceramic case 8.
  • With reference to Figs. 2A to 3B, steps of making the scintillator panel 4 will now be explained. On one surface of a rectangular substrate 10 (having a thickness of 0.5 mm) made of Al, such as the one shown in Fig. 2A, columnar crystals of Tl-doped CsI are grown by vapor deposition method, whereby the scintillator 12 is formed by a thickness of 200 µm (see Fig. 2B).
  • Since CsI forming the scintillator 12 is high in moisture absorbency so that it will deliquesce by absorbing vapor in the air if left exposed, the first polyparaxylylene film 14 is formed by CVD method in order to prevent this from occurring. Namely, the substrate 10 formed with the scintillator 12 is put into a CVD apparatus, so as to form the first polyparaxylylene film 14 by a thickness of 10 µm. As a consequence, the first polyparaxylylene film 14 is formed on all surfaces of the scintillator 12 and substrate 10 (see Fig. 2C). Since the tip portion of scintillator 12 is uneven, the first polyparaxylylene film 14 also functions to flatten the tip portion of scintillator 12.
  • Subsequently, the SiO2 film 16 is formed on the surface of first polyparaxylylene film 14 on the scintillator 12 side with a thickness of 200 nm by sputtering (see Fig. 3A). The SiO2 film 16 is formed in an area covering the scintillator 12, since it is aimed at improving the moisture resistance of scintillator 12. Since the tip portion of scintillator 12 is flattened by the first polyparaxylylene film 14 as mentioned above, the SiO2 film can be formed thinner (with a thickness of 100 nm to 300 nm) so that the output light quantity would not decrease.
  • Further, the second polyparaxylylene film 18 for preventing the SiO2 film 16 from peeling is formed with a thickness of 10 µm by CVD method on the surface of SiO2 film 16 and the surface of first polyparaxylylene film 14 not formed with the SiO2 film 16 on the substrate 10 side (see Fig. 3B). When this step is completed, the making of scintillator panel 4 ends.
  • Thereafter, the imaging device 6 is attached to the scintillator panel 4 on the scintillator 12 side with the silicone resin layer 20 interposed therebetween. Also, the bottom part of the imaging device 6 attached to the scintillator panel 4 is accommodated in the cavity portion 8a of ceramic case 8, whereas a pad portion of the imaging device 6 and a lead pin secured to the ceramic case 8 are electrically connected to each other with a bonding wire 22. Then, for protecting the bonding wire 22 and securing the scintillator plate 4 to the ceramic case 8, side wall portions of the scintillator panel 4 and imaging device 6 are fixed with the resin 24. When this step is completed, the making of the radiation image sensor 2 shown in Fig. 1 ends.
  • In the radiation image sensor 2 in accordance with this embodiment, since the scintillator 12 is covered with the first polyparaxylylene film 14 and is attached to the imaging device 6 with the silicone resin 20 interposed therebetween, the impact acting on the tip portion of scintillator 12 when bonding the scintillator panel 4 to the imaging device 6 can be alleviated by the first polyparaxylylene film 14, whereby the tip portion of scintillator 12 can be prevented from being damaged. Also, even when a distortion is generated in the substrate 10 due to temperature changes, since the scintillator 12 is covered with the first polyparaxylylene film 14, the stress acting on the scintillator 12 according to the distortion of substrate 10 can be alleviated by the first polyparaxylylene film 14, whereby the scintillator 12 can be prevented from being damaged.
  • Also, since the side walls of scintillator panel 4 and imaging device 6 are fixed with the resin 24, the connection between scintillator panel 4 and imaging device 6 can be made firm.
  • Though the silicone resin 20 is used as the matching oil (optical coupling material) in the above-mentioned embodiment, it is not restrictive; and epoxy resin, silicone oil, and the like may also be used.
  • Though the side wall portions of scintillator panel 4 and imaging device 6 are fixed with one piece of resin 24 in order to protect the bonding wire 22 and secure the scintillator plate 4 to the ceramic case 8, separate resins may be used for protecting the bonding wire 22 and for securing the scintillator plate 4 to the ceramic case 8.
  • Also, though the SiO2 film is used as the transparent inorganic film 16, it is not restrictive; and inorganic films made from Al2O3, TiO2, In2O3, SnO2, MgO, MgF2, LiF, CaF2, SiNO, AgCl, SiN and the like may also be used.
  • Though CsI(Tl) is used as the scintillator 12 in the above-mentioned embodiment, it is not restrictive; and CsI(Na), NaI(Tl), LiI(Eu), KI(Tl), and the like may also be used.
  • Though a substrate made of Al is used as the substrate 10 in the above-mentioned embodiment, any substrate can be used as long as it has a favorable X-ray transmissivity, whereby substrates such as those made of amorphous carbon mainly composed of carbon, those made of C (graphite), those made of Be, those made of SiC, and the like may also be used.
  • Though the scintillator 12 is covered with the first polyparaxylylene film 14, SiO2 film 16, and second polyparaxylylene film 18 in the above-mentioned embodiment, it may be covered with the first polyparaxylylene film 14 alone or with the first polyparaxylylene film 14 and SiO2 film 16. Since the first polyparaxylylene film 14 in contact with the scintillator 12 has an elasticity, the scintillator 12 can also be prevented from being damaged in this case as in the radiation image sensor 2 in accordance with the above-mentioned embodiment.
  • Though the imaging device 6 is used in the above-mentioned embodiment, a cooling type imaging device (C-CCD) may also be used. In this case, since the stress acting on the scintillator increases upon drastic temperature changes, the scintillator damage prevention effect of the elastic organic film becomes greater.
  • As the polyparaxylylene film in the above-mentioned embodiment, not only polyparaxylylene but also polymonochloroparaxylylene, polydichloroparaxylylene, polytetrachloroparaxylylene, polyfluoroparaxylylene, polydimethylparaxylylene, polydiethylparaxylylene, and the like can be used.
  • According to the radiation image sensor of the present invention, since the scintillator is covered with an elastic organic film and is superposed onto the imaging device with a matching oil interposed therebetween, the impact acting on the scintillator can be alleviated by way of the elastic organic film when superposing the scintillator panel onto the imaging device, whereby the scintillator can be prevented from being damaged. Also, even when a distortion is generated in the substrate due to temperature changes, since the scintillator is covered with the elastic organic film, the stress acting on the scintillator according to the distortion of substrate can be alleviated by the elastic organic film, whereby the scintillator can be prevented from being damaged.
  • Industrial Applicability
  • As in the foregoing, the radiation image sensor in accordance with the present invention is suitably usable for medical and industrial X-ray photography and the like.

Claims (2)

  1. A radiation image sensor comprising a scintillator panel and an imaging device;
    wherein said scintillator panel comprises a radiation-transparent substrate, a scintillator formed on said substrate, and an elastic organic film covering said scintillator; and
    wherein said scintillator panel and said imaging device are superposed on each other with an optical coupling material interposed therebetween, side wall portions of said scintillator panel and imaging device being firmly attached to each other with a resin.
  2. A radiation image sensor according to claim 1, wherein said scintillator has a columnar structure.
EP99925376A 1998-06-19 1999-06-18 Radiation image sensor Expired - Lifetime EP1115011B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP17308098 1998-06-19
JP17308098A JP3789646B2 (en) 1998-06-19 1998-06-19 Radiation image sensor
PCT/JP1999/003263 WO1999066347A1 (en) 1998-06-19 1999-06-18 Radiation image sensor

Publications (3)

Publication Number Publication Date
EP1115011A1 true EP1115011A1 (en) 2001-07-11
EP1115011A4 EP1115011A4 (en) 2002-09-04
EP1115011B1 EP1115011B1 (en) 2006-11-22

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US (1) US6469305B2 (en)
EP (1) EP1115011B1 (en)
JP (1) JP3789646B2 (en)
KR (1) KR100639845B1 (en)
CN (1) CN1138157C (en)
AU (1) AU4168099A (en)
DE (1) DE69934126T2 (en)
WO (1) WO1999066347A1 (en)

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US7034306B2 (en) 1998-06-18 2006-04-25 Hamamatsu Photonics K.K. Scintillator panel and radiation image sensor
US7126130B2 (en) 2001-12-06 2006-10-24 General Electric Company Direct scintillator coating for radiation detector assembly longevity
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DE69934126T2 (en) 2007-09-20
US6469305B2 (en) 2002-10-22
EP1115011A4 (en) 2002-09-04
AU4168099A (en) 2000-01-05
CN1138157C (en) 2004-02-11
JP3789646B2 (en) 2006-06-28
KR100639845B1 (en) 2006-10-27
DE69934126D1 (en) 2007-01-04
KR20010052994A (en) 2001-06-25
US20010023924A1 (en) 2001-09-27
WO1999066347A1 (en) 1999-12-23
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CN1305594A (en) 2001-07-25
EP1115011B1 (en) 2006-11-22

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